Fluorinated dialkylbenzenes



Patented Mar. 29, 19 49 UNITED STATES PATENT OFFICE FLUORINATED DIALKYLBENZENES N Drawing. Application January 8, 1946, Serial No. 639,905

4 Claims.

This invention relates to certain-halodialkylbenzen'es and more particularly to the 1-polychlorofluoroisopropyl 4 (trifluoromethybbenzenes and their derivatives which contain halogen atoms attached to the ring. The compounds concerned herein have the following structural formula:

wherein m is an integer from zero to six, inclusive; n is an integer from seven to one, inclusive; the sum of m plus 11. being seven; and wherein X is either hydrogen or chlorine.

The compounds of this series, in gener l, are colorless liquids, insoluble in water, the lowest member of which, i. e., l-heptafluoroisopropyll-(trifiuoromethyl)benzene, .boils at about 130 degrees centigrade. Other members of the series boil at successively higher temperatures depending upon the number of chlorine atoms therein. All of the compounds have relatively low freezing points, e. g., 7 to 61 degrees centigrade, and exhibit stability in the presence of aluminum foil and water.

The compounds, in general, may be prepared by the photochemical chlorination of the side chains of para-cymene or para-(chloromethyl) isopropylbenzene and the subsequent replacement of chlorine by fluorine in such a manner that the number of fluorine atoms in the methyl group is three and the number of fiuorine atoms in the isopropyl group is from one to seven, inclusive. The chlorination may be conducted at a moderately elevated temperature, for example, 175 degrees centigrade, in the presence of actinic light. Fluorination may be effected in any one of several ways, e. g., by reaction of the chlorinated product with hydrogen fiuoride in the presence of antimony pentachloride or with antimony trifluoride and a pentavalent antimony salt.

To obtain ring-chlorinated derivatives, e. g., 1 perhaloisopropyl 4 (trihalomethy1)chlorobenzenes the 1 heptachloroisopropyl 4 (trichloromethyDbenzene may be further chlorinated in the presence of ferric chloride and the resulting products may be subsequently fin orinated. The organic reaction product may then be washed with dilute acid and with water, steam-distilled, dried, and rectified, or treated in any other suitable manner to identify or separate the desired compounds.

The following examples illustrate several Ways in which members of this new class of compounds may be prepared, but are not to be construed as limiting.

Example 1 Five hundred milliliters of para-cymene was placed in a vertical chlorination tube, comprising a four-foot length of iii-millimeter glass tubing equipped with a gas dispersion disc, reflux condenser and thermometer. Illumination was provided by two banks of incandescent light bulbs placed on either side of the tube. Chlorine was introduced continuously at a rate of about two moles per hour. After a short induction period, the reaction mixture was cooled by lowering the tube into an ice-water bath. After three hours, the ice was allowed to melt, and. the reaction was continued in a water bath for an additional twelve-hours. The tube was then removed from the bath and the reaction temperature gradually raised to about 175 degrees centigrade until chlorination was complete. 1- heptachloroiscpropyl (trichloromethyDbenzene was obtained from the reaction mixture and purified by crystallization from a mixture of benzene and methanol.

Two hundred forty grams of the l-heptachloroisopropyl 4 (trichloromethyl)benzene, 180 grams of antimony trifluoride and grams of antirnony-dichlorofiuoride were introduced into an iron reactor fitted with an air-cooled iron condenser. The mixture was heated at 200 degrees centigrade for twelve hours, after which the organic product was washed with hydrochloric acid and with water until free from antimony salts, distilled under reduced pressure, and rectified. The rectification yielded three main products: (a) l-heptafiuoroisopropyl-l-(trifluoromethyl)loenzene, boiling at degrees centigrade at 748 millimeters of mercury pressure absolute, having a freezing point of -21 degrees centigrade, a refractive index at 20 degrees centigrade of 1.3861, a specific gravity at 26/4 of 1.4127, and a fluorine analysis of 60.2 per cent compared to the theoretical value of 60.5 per cent; (1)) 1-chlorohexafiuoroisopropyl-4-(trifiuoromethybbenzene; and, (c) l-dichloropentafluoroisopropyli- (trifiuoromethyl) benzene.

Example 2 One kilogram of 1-heptachloroisopropyl-4- (trichloromethyl)benzene, prepared in a manner analogous to that outlined in Example 1, and 1 kilogram of antimony pentachloride were placed in a three-liter nickel pot equipped with stirrer, inlet tube, and a nickel dephlegmator. The reaction mixture was heated to 100 degrees centigrade and 800 grams of hydrogen fluoride was introduced into the reactor at a rate of 330 grams per hour. Effluent gases were led into a collection train comprising two copper traps connected in series, the first cooled with air and the second cooled in a trichloroethylene-Dry Ice bath. In this way loss of organic material through entrainmentwasminimized. When-all; of the hydrogen fluoride had been introduced, three moles of chlorine was allowed to enter the reactor over a thirty-five minute period. An additional 200 grams of hydrogen fluoride was then passed into the reaction mixture, and a temperature of 220 centigrade was maintained therein .for an additional three-hour period. Theresulting products were removed from the collection train, Washed with concentrated hydrochloric acid and with water, and steam-distilled. The crude organic. layer, weighing 520 grams, was then dried and rectified. The following compounds were ob tained from the rectification:

4 wherein m is an integer from zero to six, inclusive; n is-an integer fromseven to one inclusive; the sum of m plus 17. being seven; and wherein X is selected from the group consisting of hy drogen and chlorine.

2. 1 heptafluoroisopropyl 4 (trifluoromethyDbenzene.

3. A- 1-dichloropentafluoroisopropyl-L(trifluoromethyllbenzene, CF3C6H4C3F5C12.

4. A 1-trichlorotetrafiuoroisopropyl-4 (trifiuoromethyl) chlorobenzene, CF3C6H3CIC3F4C13.

EARL T. MCBEE. OGDEN R. PIERCE.

S 01, percent 1*, percent o 1113 p Compound B. R, F. P., *0. 26/4 Theor. Fd. Thcor. Fd.

4-OF3CsH4-1SOC3C1F0 161.5 (7 8 mm.)-. 6l.0 1. 4095 1. 4346 10. 7 10. 0 51. 7 50.9 4-CF CeH4-1SOCQCIZF5 1. 4292 1. 5243 20. 5 20. 6 '43. 8 42. 7 4-GF5C5H1- soO3OhF4 1.4609 1. 5617 29. 3 29. 6 36.6 35.3 4-CFzC5H4-1S0QaCh a 1. 4928 1. 6163 37. 4 37. 4 30. 1 29. 8 4-OFaC0H;,Cl-1 SOC5C10F4 236.2 (7 8 m.) glass 20 1. 4780 1. 5990 35. 7 35. 4 33. 4 32.6 4-CFzCuHnC12-1SOCaC13F-1 59.0 (7 8 1.) glass -10 1.4972 1. 6180 41.0 40. 8 30.8 29. 9

U0 1. A halodialkylbenzene having the following structural formula F30 is0C C1mF,.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,005,712 Holt et al June 18, 1935 2,121,330 Scherer et a1 June 21, 1938 35. 2,174,512 Holt et al Oct. 3, 1939 2,378,453 Weinmayr June 19, 1945 

